Certain cyclopropane carboxylic acid esters as insecticides

ABSTRACT

1. AN INSECTIDAL COMPOSITION COMPRISING AN INSECTICIDALLY EFFECTIVE AMOUNT OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OFF OPTICALLY ACTIVE AND RACEMIC MIXTURES OF A COMPOUND OF THE FORMULA   1-((-CO-X-CH2-CH2-)&gt;C=CH-),2-(R-OOC-),3,3-DI(H3C-)-   CYCLOPROPANE   WHEREIN X IS SELECTED FROM THE GROUP CONSISTING OF OXYGEN AND SULFUR AND R IS SELECTED FROM THE GROUP CONSISTING OF ALKYL OF 1 TO 6 CARBON ATOMS, A RADICAL OF THE FORMULA   -CH2-(FURYLENE)-CH2-Y3   WHEREIN Y3 IS PHENYL, AND A RADICAL OF THE FORMULA WHEREIN Z IS SELECTED FROM THE GROUP CONSISTING OF ALKENYL OF 2 TO 7 CARBON ATOMS AND ALKADIENYL OF 4 TO 7 CARBON ATOMS; AND AN INERT CARRIER.

3,842,177 CERTAIN CYCLOPROPANE CARBOXYLIC ACID ESTERS AS INSECTICIDES Jacques Martel, Bondy, and Jean Buendia, Bois, France, assignors to Roussel-UCLAF, Paris, France No Drawing. Continuation-impart of abandoned application Ser. No. 306,404, Nov. 14, 1972, which is a division of application Ser. No. 48,488, June 22, 1970, now Patent No. 3,714,153. This application Feb. 5, 1973,

Ser. No. 329,847

Int. 'Cl. A01n 9/12, 9/22, 9/24 U.S. Cl. 424274 14 Claims ABSTRACT OF THE DISCLOSURE Novel insecticidal compositions having as the active ingredient, a 3,3-dirnethyl 2 (2'-oxo-3-x-cyclopentyli denemethyl)-l-cyclopropanecarboxylic acid ester of a cis or trans structure, in the form of racemic mixtures or optically active isomers of the formula wherein X is selected from the group consisting of oxygen and sulfur and R is selected from the group consisting of lower alkyl of 1 to 6 carbons, a radical of the formula wherein Y is aryl such as phenyl, and a radical of the formula CH3 Z wherein Z is alkenyl or alkadienyl such as allyl, butenyl and pentadienyl and their preparation and methods of combatting insects.

PRIOR APPLICATIONS This application is a continuation-in-part of application Ser. No. 306,404 filed Nov. 14, 1972 now abandoned which in turn is a division of application Ser. No. 48,488 filed June 22, 1970, now U.S. Pat. No. 3,714,153.

OBJECTS OF THE INVENTION United States Patent 0 THE INVENTION The novel insecticidal compositions of the invention are comprised of an effective amount of at least one member of the group consisting of racemic mixture or optically active isomers of cis or trans 3,3-dimethyl-2-(2'- oxo-3'-x-cyclopentylidenemethyl) 1 cyclopropanecarboxylic acid est-er of the formula C- COOR wherein X is selected from the group consisting of oxygen and sulfur and R is selected from the group consisting of alkyl of 1 to 6 carbon atoms, a radical of the formula -CHzi" -itCHz-Ya wherein Y is aryl, and a radical of the formula CH:|-C=CZ wherein Z is alkenyl of 2 to 7 carbon atoms or alkadienyl of 4 to 7 carbon atoms and an inert carrier.

The compositions possess interesting insecticidal prop erties which make them useful in the agricultural field and in the home against harmful insects. The elevated insecticidal activity of the compositions in which the active compound has a cis configuration is particularly notable since in compounds of pyrethrinoid structure, the derivatives of trans configuration have the important insecticide activity. The compositions with S-benzyl-3-furylmethyl ester of 3,3-dimethyl-2-(2'-oxo-3'-oxa-cyclopentylidenemethyl)-1-cyclopropanecarboxylic (IR, 28) acid are endowed with a knockdown effect against domestic flies about 2 times more intense than those with dl-allethrolonyl ester of d-trans chrystanthemic acid or dl-allethrolonyl ester of d-trans pyrethric acid.

The cyclopropanecarboxylic acid esters of formula I can be prepared by reacting 3,3-*dimethyl-2-formyl-1 cyclopropanecarboxylic acid of a cis or trans structure, racemic or optically active isomer, in the presence of a strong base with a phosphorium salt containing a 2-oxo-.

3-oxa-cyclop-entyl group which exists in a basic media in the form of an ylide, or in a neutral medium with a 2- oxo-3-X-cyclopentylidene triaryl phosporane to obtain 3,3-dimethyl-2-(2 oxo-3'-X-cyclopentylidenemethyl)-lcyclopropanecarboxylic acid of the same configuration in the 1 and 2 positions as the starting compound. The said compound can be transformed into other derivatives by reacting the acid or a functional derivative thereof with an alcohol to form the desired ester of the same configuration in the l-and 2-positions of the starting acids.

Examples of salts of the phosphonium compound containing a 2-oXo 3 X-cyclopentyltriaryl phosphonium group are a salt of (2-oxo-3-X-cyclopentyl)triaryl phosphonium such as the iodide or bromide of (2-oXo-3-X- cyclopentyl) triphenyl phosphonium which in the presence of a base gives rise to a (2-oxo-3-X-cyclopentylidene) triphenyl phosphorane and salts of (2-oxo-3-X-cyclopentyl)bis-(dialkylamino)-aryl phosphonium or of 3 (2-oxo 3 X-cyclopentyl) (dialkylamino) diaryl phosphonium.

Among the strong bases in the presence of which the condensation of the phosphonium salt with 3,3-dimethyl- 2-formyl-l-cyclopropanecarboxylic acid is eifected are alkali metal hydrides such as sodium hydride, alkali metal amides such as sodium amide, alkali metal alcoholates such as sodium methanolate, sodium ethanolate or potassium tert.-butylate or alkyl lithiums such as methyl lithium.

The said condensation is conveniently effected in an organic solvent or mixture of organic solvents such as methanol, ethanol, methylene chloride, dichloroethane, chloroform, monoethyl ether of diethyleneglycol, diethyl ether of diethyleneglycol, ethyl ether, dimethylsulfoxide, tetrahydrofuran, dimethoxyethane or dimethyl formamide.

A preferred mode of the process consists of using as the phosphorus reactant containing the 2-oxo-3-X-cyclopentyl group, a 2-oxo-3-X-cyclopentylidene triaryl phosphorane and notably a 2-oxo-3-X-cyclopentylidene triphenyl phosphorane. This condensation is effected in the absence of a basic agent when using an aprotic polar solvent such as tetrahydrofuran.

2-oxo-S-X-cyclopentylidene triphenyl phosphorane can be prepared by the action of a base such as sodium carbonate, potassium carbonate or sodium hydroxide on a halide of 2-oxo-3-X-cyclopentyl triphenyl phosphonium such as described by Fliszar et al. Helv. Chim. Acta, Vol. 46 (1963) p. 1580.

After the condensation of 3,3-dimethyl-2-formyl-l-cyclopropanecarboxylic acid with the phosphonium salt or the phosphorane, the 3,3-dimethyl-2-(2-oxo-3'-X-cyclopentylidenemethyl)-l-cyclopropanecarboxylic acid may be purified such as by eliminating the non reacted aldehyde fraction by treatment with reagent T or by transforming the acid into a salt, particularly a salt of an optically active base and purifying the diastereoisorneric salt by crystallization to obtain after acidification with an acid the pure acid.

To obtain an ester of the said acid, the acid chloride is reacted with an alcohol in the presence of a tertiary amine such as pyridine or triethylamine in an organic solvent such as benzene or toluene. The acid chloride can be formed easily by the action of oxalyl chloride with an alkali metal salt of the said acid, such as the potassium salt. The alkali metal salts of the acid can themselves be made by reacting stoichiometric quantities of the acid and an alkali metal methylate or alkali metal hydroxide.

The esterification can also be effected by using the acid anhydride or mixed acid anhydride as the functional derivative of the acid. The esters may be obtained by reacting the acid chloride with an alkali metal derivative of the desired alcohol.

The insecticidal compositions of the invention may also contain one or more other pesticide agents. The compositions may be in the form of powders, granules, suspensions, emulsions, solutions, aerosol solutions, combustible tapes or other preparations classically used for compositions of this type.

In addition to the active ingredients, the compositions generally contain a vehicle and/or non-ionic, surfaceactive agent to assure a uniform dispersion of the components of the mixture. The vehicle may be a liquid such as water, alcohol, hydrocarbons or other organic solvents, mineral, animal or vegetable oils, powders such as talc, clays, silicates, kieselguhr, etc.

To increase the insecticidal activity of the compositions, classical synergistic additives such as 1-(2,5,8-trioxadodecyl)-2-propyl-4,S-methylenedioxy benzene (butoxide of piperonyl N- Z-ethylheptyl -bicyclo (2,2,1 )-5-heptene- 2,3-dicarboximide, etc., may be added thereto. The compositions preferably contain 0.2 to 90% by weight of the active component. A preferred example of the composition is an emulsifiable concentrate of about 1% by weight of 4 the 5-benzyl-3-furyl-methyl ester of 3,3-dimethyl-2-(2'- oxo-3'-oxa-cyclopentylidenemethyl) 1 cyclopropanecarboxylic (1R,2S) acid, 10% of butoxide of piperonyl, 5% of Tween 80, 83.9% of xylene and 0.1% of Topanol A (2,4-dimethyl-6-tert.-butyl-phenol).

The compositions of the invention have been found to be effective in combatting domestic or household insects such as house flies and cockroaches; for killing insects which infest stored grain as in silos such as Sitophilus granarius; and for combatting insects which attack growing crops in the field such as caterpillars. The three methods of combatting insects comprises contacting the insects with a lethal amount of at least one compound of formula I alone or with other pesticidal agents.

Racemic mixtures and optically active isomers of 3,3- dimethyl-Z-forrnyl l cyclopropanecarboxylic acids of the cis and trans structure may be obtained by the process described in French Pat. No. 1,580,475. Trans 3,3-dimethyl-Z-formyl-l-cyclopropanecarboxylic (1S,2S) acid is obtained by treating l-trans chrysanthemic (1S,2S) acid with ozone at a low temperature in methanol and then effecting reductive decomposition of the oxidation product with methyl sulfide. The corresponding (1R,2R) acid or racemic (1RS,2RS) acid can be obtained in an analogous fashion from d-trans chrysanthemic (1R, 2R) acid or racemic trans chrysanthemic lRS, 2R8) acid.

Cis 3,3-dirnethyl-2-formyl-1 cyclopropanecarboxylic (1S, 2R) acid can be prepared by reacting methanol with trans 3,3-dimethyl-2-formyl 1 cyclopropanecarboxylic (18, 2S) acid, eliminating the water from the reaction medium with a physical agent such as anhydrous alkali metal aluminosilicate, treating the resulting dimethyl ketal of trans 3,3-dimethyl-2-formyl 1 cyclopropanecarboxylic (18, 2S) acid with p-toluene sulfonic acid to simultaneously eliminate methanol from the reaction medium by physical means to obtain the lactone of the methyl hemiketal of cis 3,3-dimethyl-2-formyl-l-cyclopropanecarboxylic (1S, 2R) acid and hydrolyzing the said lactone by heating in a mixture of water and dioxane to obtain cis 3,3-dimethyl-2formyl 1 cyclopropanecarboxylic (1S, 2R) acid which exists in the form of internal hemiacylal. In analogous manner, trans 3,3-dirnethyl-2-formyll-cyclopropanecarboxylic (1R, 2R) acid and racemic trans 3,3-dimethyl-2-formyl l cyclopropanecarboxylic (lRS, 2RS) acid can be reacted to obtain cis 3,3-dimethyl- 2-formyl-l-cyclopropanecarboxylic (1R, 2S) acid and racemic cis 3,3-dimethyl-2-formyl-l-cyclopropanecarboxylic (IRS, 2RS) acid, respectively.

Cis or trans, racemic or optically active 3,3-dimethyl-2- formyl-l-cyclopropane carboxylic acids can be prepared by a variation of the process of the said patent by treating methyl esters of chrysanthemic acids by an analogous set of reactions.

In the following examples there are described several preferred embodiments to illustrate the invention. However, it should be understood that the invention is not intended to be limited to the specific embodiments.

EXAMPLE I Preparation of Hemiacylal of Cis 3,3-dimethyl-2-formyll-cyclopropanecarboxylic (1S,2R) Acid Step A: Trans 3,3-dimethyl-2-formyl-l-cyclopropanecarboxylic (1S,2S) acid.-2O gm. of l-trans chrysanthemic (18, 2S) acid were dissolved in 250 cc. of methanol and after cooling to C., a current of ozonized oxygen was bubbled through the solution until a blue coloration appeared. A current of oxygen was then bubbled therethrough for 15 minutes, followed by a current of nitrogen for 45 minutes. 10 cc. of dimethyl sulfide were slowly added to the reaction mixture and the temperature was maintained at 35 C. for 30 minutes, then one hour at 0 C. and finally one hour at room temperature. The solvent was removed by distillation at a reduced pressure and the residue was added to a solution of 17 gm. of trimethylamino acetohydrazide chloride (Reagent T) in 170 cc. of ethanol and 17 cc. of acetic acid. The reaction mixture was heated to reflux and held there for one hour, then was cooled. A dilute solution of sodium hydroxide Was added to the reaction mixture which was then extracted with ether to remove any non-aldehyde fraction. The solution was made acidic with dilute aqueous hydrochloric acid and was extracted with ether. The ether solution was washed, dried and concentrated to dryness. The residue was empasted with petroleum ether (b.p.=35-75 C.) to obtain 5.80 gm. of trans 3,3-dimethyl-2-formyl-lcyclopropane carboxylic (18, 2S) acid.

Step B: Dimethyl ketal of trans 3,3-dimethyl-2-formyll-cyclopropane carboxylic (18, 2S) acid.13.8 gm. of trans 3,3 dimethyl-Z-formyl-l-cyclopropane carboxylic (18, 2S) acid were added to 100 cc. of methanol under a nitrogen atmosphere and the resulting solution was refluxed for 22 hours with recycle of distillate through a column packed with siliporite (dehydrated alkali metal aluminum silicate) and was then concentrated to dryness to recover crystals impregnated with an oil impurity which was removed by vacuum filtration. The crystals were added to petroleum ether (b.p.=67-75 C.) and vacuum filtered and dried to obtain 11.7 gm. of dimethyl ketal of trans 3,3-dimethyl-2-formyl-1-cyclopropane carboxylic (18, 2S) acid melting at 65 C.

Analysis.-C H O molecular weight=188.22. Calculated: percent C, 57.43; percent H, 8.57. Found: percent C, 57.6; percent H, 8.5.

Step C: Lactone of Methyl hemiketal of cis 3,3-dimethyl 2 formyl-l-cyclopropane carboxylic (1S, 2R) acid.5 gm. of the dimethyl ketal of trans 3,3-dimethyl- 2 formyl-l-cyclopropane carboxylic (15, 2S) acid and 0.21 gm. of p-toluene sulfonic acid were introduced under a nitrogen atmosphere into 175 cc. of benzene and the reaction mixture was heated to reflux and maintained there for distillation and the volume of the reaction mixture was kept constant by the continuous addition of benzene. After about 6 hours and cooling, the benzene was removed by distillation and the reaction mixture was added to an aqueous solution of sodium bicarbonate containing ice. The reaction mixture was then extracted with ether and concentrated to dryness to obatin 1.9 gm. of the lactone of methyl hemiketal of cis 3,3-dimethyl-2- formyl-l-cyclopropanecarboxylic (1S, 2R) acid having a boiling point of 60 C. at 0.3 mm. Hg.

IR Spectrum.(CHCl Confirmed the absence of a free OH and showed a band at 1764 corresponding to a carbonyl of a y-lactone.

Step D: Cis 3,3-dimethyl-2-formyl-l-cyclopropanecarboxylic (1S, 2R) acid in form of internal hemiacetal.- 1.9 gm. of the lactone of methyl hemiketal of cis 3,3-dimethyl-Z-formyl-l-cyclopropanecarboxylic (1S, 2R) acid were added to a mixture of 25 cc. of water and 12.5 cc. of dioxane and the mixture was maintained at 60 C. for 1 hour and then concentrated to dryness at reduced pressure to obtain 0.55 gm. of cis 3,3-dimethyl-2-f0rmyll-cyclopropanecarboxylic (1S, 2R) acid melting at 114 C. in the form of an internal hemiacylal. A sample of the product recrystallized from isopropyl ether had a melting point of 116 C. and a specific rotation [a] =+103 '(C=1% in methanol).

EXAMPLE II procedure of step B of Example I, the said compounds were reacted with methanol to form the dimethyl ketal of trans 3,3 dimethyl-Z-formyl-l-cyclopropanecarboxylic (1R, 2R) acid melting at 65 C. and the dimethyl ketal of racemic trans 3,3 dimethyl-Z-formyl-l-cyclopropanecarboxylic (IRS, 2RS) acid, respectively.

Using the process of Step C of Example I, the said dimethyl ketals were treated to obtain the lactone of the methyl hemiketal of cis 3,3 dimethyl-Z-formyl-l-cyclopropanecarboxylic 1R, 2S) acid and the lactone of the methyl hemiketal of cis 3,3 dimethyl-Z-formyl-l-cyclopropane carboxylic (IRS, ZSR) acid, respectively.

Using the procedure of Step D of Example I, the said lactones were reacted to obtain the internal hemiacylal of cis 3,3 dimethyl-Z-formyl-l-cyclopropanecarboxylic (1R, 2S) acid melting at 116 C. and having a specific rotation [1x] =102 (c=l% in ethanol) and the internal hemiacylal of racemic cis 3,3-dimethyl-2-formyll-cyclopropanecarboxylic (IRS, 2SR) acid, respectively.

EXAMPLE III Cis 3,3 dimethyl-2-(2'-oxo-3'-oxa-cyclopentylidenemethyl)-cyclopropanecarboxylic 1R, 2S) acid.

A solution of 13.2 gm. of (2-oxo-3-oxa-cyclopentyl) triphenylphosphonium bromide (Fliszar et al, Helv. 46 (1963) p. 1580] in 50 cc. of methylene chloride was added under a nitrogen atmosphere to a solution of 2.1 gm. of sodium methanolate in 20 cc. of methanol and then the reaction mixture was heated to reflux and held there for 30 minutes. 2.2 gm. of the internal hemiacylal of cis 3,3 dimethyl 2-formyl-lcyclopropanecarboxylic (1R, 2S) acid diluted with 30 cc. of methylene chloride were added to the reaction mixture and held at reflux for an other 1% hours. The reaction mixture was cooled and a saturated aqueous solution of sodium bicarbonate was added thereto. The neutral fractions were eliminated by extraction with methylene chloride and the aqueous phase was made acidic with concentrated aqueous hydrochloric acid solution. The mixture was saturated with sodium chloride and extracted with ethylether. The combined ether extracts were dried and concentrated to dryness under reduced pressure. The residue was added to 1.9 gm. of Reagent T, 1.9 cc. of ethanol and 1.9 cc. of acetic acid and the reaction mixture was heated to reflux and held there for 1 hour. The reaction mixture was poured into a mixture of water, ice and 3 cc. of 10 N aqueous sodium hydroxide and the non-aldehydic fraction was extracted with ethyl ether. The ether extracts were dried and concentrated to dryness under reduced pressure. The residue was crystallized from a mixture of isopropylether-methanol (3:1) to obtain 0.40 gm. of cis 3,3-dimethyl-2-(2- oxo-3'-oxa-cyclopentylidenemethyl)-1 cyclopropanecarboxylic (IR, 25.) acid melting at 177 C. and having a specific rotation [a] =+22 (c=0.59% in ethanol). A second crop of 0.18 gm. of product melting at 176 C. was obtained from the mother liquors. The first crop was analyzed:

Analysis.C H O molecular wcight=210.23: Calculated: percent C, 62.84; percent H, 6.71. Found: percent C, 62.7; percent H, 6.6.

U.V. Spectrum (ethanol): A at 245-246 ma 6: 15,700.

In an analogous manner, the corresponding (1S, 2R) acid and the racemic (lSR, 2R8) acid were reacted to obtain, respectively, cis 3,3-dimethyl-2-(2'-oxo-3'-oxa-cyclopentylidenemethyl)-1 cyclopropanecarboxylic (1S, 2R) acid melting at 177 C. and having a specific rotation [a] =21 (c=0.59% in ethanol) and racemic cis 3,3 dimethyl 2 (2'-oxo-3'-oxa-cyclopentylidenemethyl)-l-cyclopropranecarboxylic (lSR, 2RS) acid.

As far as is known, these three compounds are not described in the literature.

EXAMPLE IV Cis 3,3 dimethyl 2 (2'-oxo-3'-oxa-cyclopentylidenemethyl)-1-cyclopropanecarboxylic (IR, 28) acid 5.5 gm. of 2'-oxo-3'-oxa cyclopentylidenetriphenylphosphorane [Fliszar et al., Helv. Chim. Acta, Vol. 46 (1963), p 1580] were added under a nitrogen atmosphere to 250 cc. of tetrahydrofuran and the reaction mixture was heated to reflux. After the addition of 2.26 of the internal hemiacylal of cis 3,3-dimethyl-Z-formyl-l-cyclopropanecarboxylic (IR, 25) acid, diluted with 10 cc. of tetrahydrofuran the reflux was maintained for 6 hours. The tetrahydrofuran was distilled off under reduced pressure and methylene chloride was added to the residue. The acid form was extracted with a saturated aqueous solution of sodium bicarbonate and the combined aqueous phases were washed with methylene chloride and was acidified with aqueous concentrated hydrochloric acid. The acid aqueous phase was extracted with methylene chloride and the combined methylene chloride extracts were dried and concentrated to dryness by distillation under reduced pressure to obtain 3.1 gm. of cis 3,3-dimethyl- 2-(2-oxo-3'-oxa-cyclopentylidenemethyl) 1 cyclopropane carboxylic (IR, 25) acid melting at 177 C. and having a specific rotation [a] =|22 (c=0.59% in ethanol). It was identical to the compound obtained in Example III.

EXAMPLE V 5-benzyl-3-furylmethyl ester of cis 3,3 dimethyl-2-(2'- xo-3'-oxa-cyclopentylidenemethyl)-1 cyclopropanecarboxylic (IR, 28) acid Step A.0.520 gm. of cis 3,3-dimethyl-2-(2'-oxo-3'- oxa cyclopentylidenemethyl) 1 cyclopropanecarboxylic (1R, 2S) acid was added under a nitrogen atmosphere to 2 cc. of methanol and then an amount of a methanolic solution of potassium hydroxide was added dropwise in the presence of phenolphthalein until the pink color of phenolphthalein occurred. The methanol Was removed by distillation under reduced pressure, then with the addition of benzene and distillation under reduced pressure to obtain the potassium salt of cis 3,3-dimethyl- 2-(2-oxo-3-oxa cyclopentylidenemethyl) 1 cycloprocarboxylic (1R, 2S) acid As far as is known, this compound is not described in the literature.

Step B.--The potassium salt obtained in Step A was added to cc. of benzene and after the addition of 0.5 cc. of pyridine thereto under a nitrogen atmosphere, then a solution of 0.630 gm. of oxalyl chloride in 5 cc. of benzene was added dropwise. The insolubles were removed by filtration and after stirring the solution for one hour at room temperature, the solvent was distilled off under reduced pressure then with the addition of benzene and distillation under reduced pressure to obtain cis 3,3-dimethyl-Z-(2.-oxo-3-oxa-cyclopentylidenemethyl) 1 cyclopropanecarboxylic (IR, 25) acid chloride.

As far as is known, this compound is not described in the literature.

Step C.-A solution of 0.515 gm. of 5-benzyl-3-furylmethanol in 5 cc. of benzene and 0.5 cc. of pyridine were added dropwise at +5 C. to a suspension of the acid chloride Step B in 10 cc. of benzene and the mixture was stirred for hours at room temperature. The reaction mixture was poured into a mixture of 50 cc. of aqueous 2N hydrochloric acid solution and ice and the benzene phase was recovered by decantation and was washed successively with water, a saturated aqueous sodium bicarbonate solution and then water. The aqueous phase was extracted with ethyl ether and the combined organic phases were dried, and concentrated to dryness under reduced pressure. The residue was purified by chromatography and silica gel column impregnated with a mixture of benzene-ethyl acetate-triethylamine (68-3 0-2) with elution with a mixture of benezene-ethyl acetate (70-30) containing 0.2% of triethylamine to obtain 0.690 gm. of 5-benzyl-3-furylmethyl ester of cis 3,3-dimethyl-2-(2-oxo- 3-oxa cyclopentylidenemethyl) 1 cyclopropanecarboxylic (IR, 25) acid having a specific rotation 0 :L 1 (c=0.48% in ethanol).

Analysis.-C H O molecular weight=380.42: Calculated: percent C, 72.61; percent H, 6.36. Found: percent C, 72.7; percent H, 6.3.

8 U.V. Spectrum (ethanol) Am. at 224 m E}' =476 Infiex. towards 241 mu E}'Z;,, =422 As far as is known, this compound is not described in the literature.

EXAMPLE VI dl-Allethrolone ester of cis 3,3-dimethyl-2-(2'-oxo-3'-oxacyclopentylidenemethyl) 1 cyclopropanecarboxylic (1R, 2S) acid Step A.2.8 gm. of cis 3,3-dimethyl-2-(2'-oxo-3-oxacyclopentylidenemethyl 1 cyclopropanecarboxylic (IR 28) acid was reacted as in Step A of Example V to obtain the potassium salt of cis 3,3-dimethyl-2-(2-oxo-3'-oxacyclopentylidenemethyl)-1-cyclopropanecarboxylic (IR, 28) acid. The said potassium salt was treated as in Step 13 of Example V to obtain the corresponding acid chloride.

Step B.-The said acid chloride was suspended in 54 cc. of benzene and then 3 cc. of pyridine followed by 2.486 gm. of dl-allethrolone (titrating diluted with 10 cc. of benzene were added to the suspension at 5 C. under a nitrogen atmosphere. The reaction mixture was stirred for 60 hours at room temperature and was then poured into a mixture of ice and an aqueous solution of hydrochloric acid. The organic phase was separated by decantation and was then washed successively with water, a saturated aqueous sodium bicarbonate solution and then water. The aqueous phases were extracted with ether and the organic phases were combined, dried and concentrated to dryness by distillation under reduced pressure. The residue was purified by chromatography over silica gel with elution with a mixture of benzene-ethyl acetate (1-1) made alkaline with 0.5% of triethylamine to obtain 1.69 gm. of dl-allethrolone ester of cis 3,3-dirnethyl-2- (2' oxo-3-oxa-cyclopentylidenemethyl)-1-cyclopropane carboxylic (IR, 28) acid having a specific rotation [m] =6.5 (c=1.1% in ethanol).

Analysis.C I-I O molecular weight=344.40: Calculated: percent C, 69.75; percent H, 7.02. Found: percent C, 69.9; percent H, 7.3.

U.V. Spectrum (ethanol).7\ at 235 mu =24,900.

As far as is known, this compound is not described in the literature.

EXAMPLE VII Trans 3,3-dimethyl-2-(2'-oxo-3-oxa-cyclopentylidenemethyl)-1-cyclopropanecarboxylic (1R, 2R) acid In a manner analogous to Example III, 5.68 gm. of trans 3,3 dimethyl-Z-formyl-l-cyclopropanecarboxylic (1R, 2R) acid was reacted to obtain 3.08 gm. of trans 3,3dimethyl-2-(2'-oxo 3'-oxacyclopentylidenemethyl)-1- cyclopropanecarboxylic (1R, 2R) acid melting at 137 C. and having a specific rotation [a] =+57.5 (c=0.69% in ethanol).

Anqlysis.C I-I O molecular weight=210.23: Ca1- culated: percent C, 62.84; percent H, 6.71. Found: percent C, 62.6; percent H, 6.7.

In a similar fashion, trans 3,3-dimethyl-2-formyl-1- cyclopropanecarboxylic (18, 2S) acid and the corresponding racernic mixture were reacted to form trans 3,39-dimethyl-2-(2'-oxo 3' oxa-cyclopenylidenemethyl)- l-cyclopropanecarboxylic (18, 2S) acid as well as the corresponding racemate thereof.

As far as is known, the said 3 compounds have not been described in the literature.

EXAMPLE VIII Trans 3,3-din1ethyl-2-(2-oxo-3'-oxa-cyclopentylidenemethyl)-1-cyclopropanecarboxylic (1R, 2R) acid Using the procedure of Example IV, 2.26 gm. of trans 3,3 dimethyl-2-formyl-1-cyclopropanecarboxylic (1R, 2R) acid were reacted to obtain 2.885 gm. of trans 3,3-

9 dimethyl-2- (2-oxo 3' oxa-cyclopentylidenemethyl)-1- cyclopropanecarboxylic (1R, 2R) acid melting at 135 C. and having a specific rotation [a] +57.5 (c=0.69% in ethanol.) The product was identical to that of Example VII.

EXAMPLE IX Using the procedure of Example V, 2.5 gm. of trans 3,3 dimethyl-Z-(2'-oxo-3-oxa-cyclopentylidenemethyl)- l-cyclopropanecarboxylic (1R, 2R) acid were reacted to obtain 2.95 gm. of the -benzyl-3-furyl-methyl ester of trans 3,3 dimethyl-2-(2'-oxo-3'-oxa-cyclopentylidenemethyl)-1-cyclopropane carboxylic (1R, 2R) acid, in oily form having a refractive index n =1.5 630 and a specific rotation [a] =7 (c=1.2% in ethanol).

Analysis.-C H O molecular weight=380.42: Calculated: percent C, 72.61; percent H, 6.36. Found: percent C, 72.8; percent H, 6.5.

U.V. Spectrum (ethanol):

As far as is known, this compound is not described in the literature.

EXAMPLE X Using the procedure of Example VI, 2.8 gm. of trans 3,3-dimethyl-2-(2'oxo 3' oxa-cyclopenylidenemethyl)- l-cyclopropanecarboxylic (1R, 2R) acid was reacted to obtain 3.01 gm. of the dl-allethrolone ester of trans 3,3- dimethyl-2-(2'-oxo 3' oxa-cyclopentylidenemethyl)-1- cyclopropanecarboxylic (1R, 2R) acid having a specific rotation [a] =+8.5 (o=0.9% in ethanol).

U.V. Spectrum (ethanol). at 235 mp. e=25,650.

As far as is known, this compound is not described in the literature.

EXAMPLE XI Cis 3,3-dimethyl-2- (2-oxo-3'-thia-cyclopentylidenemethyl)-1-cyclopropanecarboxylic (IR, 28) acid 4.6 gm. of 2-oxo-3-thia-cyclopentylidene triphenylphosphorane [described by Zimmer et al., Tetrah. Lett. No. 52, (1968) p. 5435] and 1.8 gm. of the internal hemiacylal of cis 3,3-dimethyl-2-formyl-l-cyclopropanecarboxylic (1R, 2S) acid were added to 120 cc. of tetrahydrofuran and the reaction mixture was heated to reflux and held there for 4 hours. The tetrahydrofuran was distilled off under reduced pressure and methylene chloride was added thereto. The organic phase was extracted with an aqueous solution of sodium bicarbonate and the aqueous alkaline phase was acidified to a pH of 2 and was then extracted with methylene chloride. The methylene chloride extracts were dried and concentrated to dryness by distillation under reduced pressure. The residue was empasted with isopropyl ether to obtain 2.140 gm. of cis 3',3-dimethyl-2-(2-oxo 3' thiacyclopentylidenemethyl)- l-cyclopropanecarboxylic (1R, 2S) acid melting at 161 C.

RMN Spectrum (deuterochloroform).-The RMN spectrum is in accord with the cis configuration of the ring. It decomposed as follows:

Signals at 401 to 413 Hz. corresponding to ethylenic hydrogen. Signal at 550 Hz. corresponding to carboxyl hydrogen.

As far as is known, this compound is not described in the literature.

i0 EXAMPLE XII 5 benzyl 3 furyl methyl ester of cis 3,3-dimethyl-2- (2'-oxo 3 thia cyclopentylidenemethyl)-1-cyclopropanecarboxylic (1R, 2S) acid Step A.-1.850 gm. of cis 3,3-dimethyl-2-(2'-oxo-3'- thia-cyclopentylidenemethyl) 1 cyclopropane carboxylic (1R, 2S) acid was added to 16 cc. of methylene chloride and after the addition of 2 cc. of thionyl chloride thereto, the mixture was stirred at room temperature for 1 /2 hours. The volatile fraction was removed by distillation under reduced pressure to obtain the cis 3,3-dimethy1- 2 (2 oxo 3' thia cyclopentylidenemethyl)-1-cyclopropanecarboxylic (IR, 28) acid chloride which was used as is for the next step.

As far as is known, this compound is not described in the literature.

Step B.The acid chloride from Step A was added to a mixture of 10 cc. of benzene and 3 cc. of pyridine and then a solution of 1.54 gm. of 5-benzyl-3-furyl-methanol in 7 cc. of benzene was added thereto. The reaction mixture was stirred for 15 hours at room temperature and the precipitate formed was filtered oil. The filtrate was washed successively with an aqueous 2N hydrochloric acid solution, water, an aqueous solution of sodium bicarbonate and then water; was dried and concentrated to dryness under reduced pressure. The residue was purified by chromatography over silica gel with elution with a mixture of benzene-ethylacetate (-20) to obtain 2.650 gm. of the 5 benzyl 3 furyl-methyl ester of cis 3,3- dimethyl 2 (2' oxo 3' thia cyclopentylidenemethyl) 1 cyclopropanecarboxylic (1R, 2S) acid having a specific rotation [a] =-|-10.5 (c.'=l.0% in ethanol).

RMN Spectrum (deuterochloroform).-RMN spectrum is in accord with a cis configuration of the ring. It decomposed as follows:

Signals at 74-79 Hz. corresponding to hydrogens of 3-methyls.

Signals at -103. 5-112.5-122 Hz. corresponding to hydrogens at cyclopropyl.

Signals at 168-212 Hz. corresponding to cyclopentane hydrogens.

Signal at 235 Hz. corresponding to hydrogens of CH of the benzyl group.

Signal at 293.8 Hz. corresponding to hydrogens of CO CH group.

Signal at 362.1 Hz. corresponding to 4-hydrogen in furan ring.

Signals at 4055-4155 Hz. corresponding to ethylenic hydrogen.

Signal at 435 Hz. corresponding to hydrogens of benzene nucleus.

Signal at 449.5 Hz. corresponding to 2-hydrogen of furan ring.

As far as is known, this compound is not described in the literature.

EXAMPLE XIII Preparation of trans 3,3-dimethyl-2-(2-oxo'-3-thia-cyclopentylidenemethyl)-1-cyclopropanecarboxylic (1R,2R) acid 3.62 gm. of 2-oxo-3-thia-cyclopentylidene triphenyl phosphorane [described by Zimmer et al., Tetrah. Lett.

No. 52 (1968), p. 5435] and 1.42 gm. of trans 3,3-dimethyl-2-formyl-1-cyclopropane carboxylic (1R, 2R) acid were added to cc. of tetrahydrofuran and the reaction mixture was heated to reflux and held there for 4 hours. The tetrahydrofuran was distilled off under reduced pressure and the residue was extracted with methylene chloride. The combined methylene chloride phases were washed with an aqueous sodium bicarbonate solution and the combined alkaline aqueous phases were acidified to a pH of 2. The aqueous acid phase was extracted with methylene chloride and the organic extract was dried and concentrated to dryness under reduced pressure. The

residue was empasted with isopropyl ether to obtain 1.170 gm. of trans 3,3-dimethyl-2-(2'-oxo-3'-thia-cyclopentylidenemethyl) 1 cyclopropanecarboxylic (1R,2R) acid melting at 117 C. and having a specific rotation [a] =+52.5 (c.=1% in ethanol).

RMN Spectrum (deuterochloroform).The RMN spectrum was in accordance with the trans configuration of the ring. It decomposed as follows:

Signals at 7882.5 Hz. corresponding to hydrogens of 3- methyl Signals at 106l11.5118.5 Hz. corresponding to hydrogen at 2-position.

Signals at 124-128.5-l34 Hz. corresponding to hydrogen at l-position. Signals at 183.5-186-191 Hz. corresponding to hydrogens at '-position of the 2'-oxo-3'-thiacyclopentyl ring. Signals at 197-202 HZ. corresponding to hydrogens at 4- position of the 2'-oxo-3'-thia-cyclopentyl ring.

Signals at 369-379 Hz. corresponding to ethylenic hydrogen.

Signal at 601 Hz. corresponding to carboxyl hydrogen.

As far as is known, this compound is not described in the literature.

EXAMPLE XIV 5-Benzyl-3-furyl-methyl ester of trans 3,3-dimethyl-2-(2' oxo 3 thia-cyclopentylidenemethyl) 1 cyclopropane carboxylic (1R,2R) acid Step A.l.530 gm. of the acid of Example XXIII were added to 12 cc. of methylene chloride and after theaddition of 2 cc. of thionylchloride, the reaction mixture was stirred at room temperature for 2% hours. The volatile fraction was distilled off under reduced pressure to obtain trans 3,3-dimethyl-2-(2'-oxo-3-thia-cyclopentylidenemethyl)-1-cyclopropanecarboxylic (1R, 2R) acid chloride which was used as for the next step.

As far as is known, this compound is not described in the literature.

Step B.The acid chloride from Step A was added to cc. of benzene and 3 cc. of pyridine and a solution of 1.28 gm. of 5-benzyl-3-furyl-methanol in 5 cc. of benzene was added thereto. The reaction mixture was stirred for 15 hours at room temperature and was filtered to remove the precipitate formed. The filtrate was successively washed with a solution of 2N aqueous hydrochloric acid, water, aqueous solution of sodium bicarbonate and then water. The solution was dried and the solvent was distilled 01f under reduced pressure. The residue was purified by chromatography over silica gel with elution with a mixture of benzene-ethyl acetate (70:30). The product was empasted with isopropyl ether to obtain 1.446 gm. of the S-benzyl 3 furyl-methyl ester of trans 3,3-dimethyl 2 (2' oxo 3' thia-cyclopentylidene methyl) 1 cyclopropanecarboxylic (1R, 2R) acid melting at 133 C. and having a specific rotation [a] =--9.5 (c=0.5% in ethanol).

RMN spectrum (deuterochloroforrn) .-The RMN spectrum is in accordance with the trans configuration of the ring. It decomposed as follows:

Signals at 75-78 Hz. corresponding to hydrogens of 3- methyl.

Signals at 105.5-1 10.5-116 Hz. corresponding to hydrogen in 2-position.

Signals at 122.5127.5131 Hz. corresponding to hydrogen in l-position.

Signals at 170 and 210 Hz. corresponding to hydrogen in 5- and 4'-position of 2'-oxo-3-thia cyclopentyl ring.

Signal at 237.5 Hz. corresponding to hydrogens of CH of benzyl group.

Signal at 297.5 Hz. corresponding to hydrogens of CH of -CO CH group.

Signal at 364 Hz. corresponding to hydrogen in 4-position of furan ring.

12 Signals at 360-378 Hz. corresponding to ethylenic hydrogen. Signal at 438 Hz. corresponding to hydrogens of benzene ring. Signal at 443.5 Hz. corresponding to Z-hydrogen of furan ring.

As far as is known, this compound is not described in the literature.

INSECTICIDAL STUDY A. Knockdown Effect on Household Flies.In this test, S-benzyl 3 furyl-methyl 3,3-dimethyl-2S-(2-oxo- 3' oxa cyclopentylidenemethyl) cyclopropane 1R- carboxylate (compound AEx. V) and 5-benzyl-3-furylmethyl 3,3 dimethyl 2S (2' oxo 3' thia-cyclopentylidenemethyl) cyclopropane 1R carboxylate (compound C-Ex. XII) were compared with dl-allethrolone d-trans chrysanthemate (compound B). The products were tested by direct spraying 2 ml. of an acetone solution thereof using a Potter Table onto 20 female and male house flies 4 days old. The test was repeated 5 times for each dose and the percent of knock down insects (percent KD) was determined 2, 4, 8, 12 and 16 minutes after the spraying. In certain cases, 10 parts by weight of piperonyl butoxide per weight of active compound were used as a synergist (PB). The results are reported in Tables I, II and III.

TABLE I Percent KD after Dose in 2 4 8 16 Compound mg./liter min. min. min. min;

A plus PB 100 61. 8 98. 2 99. 2 100 50 31. 8 91. 6 100 100 25 3. 8 42. 5 86. 8 85. 8

Controls O 0 0 0 0. 9

13 plus PB 100 41. 3 87. 8 99. 2 98. 5 50 7. 6 39. 4 94. 0 5 25 2. 7 l6. 4 40. 8 43.7

TABLE II Percent KD alter Dose in mg./ 2 4 8 12 16 Compound liter min. min. min. min. min. KT D KTcn Controls 0 3. 5 1. l 2. 3 4. 7 5. 0

TABLE III Percent KD after Dose in mg./ 2 4 8 12 16 Compound liter min. min. min. min. nn'n. KT50 0 plus PB 500 94. 5 100 100 100 100 2 50 35. 7 87. 9 99. 0 100 100 2. 4

Controls 0 0 0 0 0 O B plus PB 500 63. 6 95. 5 100 100 100 1. 7 50 5. 8 23. 3 38. 8 67. 9 67. 9 8. 5

The results of Table I show that compound A has a knock down activity about twice that of compound B and Tables II and III show that compound C has a clear knock down superiority over compound B.

In a second test, the compound with and without 10 parts by weight of piperonyl butoxide as synergist were topically applied to the dorsal thorax of 50 female house flies in a 1 microliter of acetone solution. Each dose was repeated 3 times and the percent of dead flies after 24 3,842,177 13 14 hours was determined. The results are reported in Table Table V shows that compound A in the synergistic IV mixture used in the test is about 8 times more active as an insecticide than compound B in the synergistic mixture.

Dose in Percent mg./l. mortality DLao 5 TABLE IV Compound mm m mm m 1 t. 5 04 1 3 1 a I .n 1N7 1 u u m 9 9 0 m mm m 1 mm M H 8 6401 2 m0 3 "m3 Q 1 D m 99 4 7 "M T. K 6 0963 0 09 t l e n c I n V n D 0565 5 6 L H B P 4m 0002 on 05 A 4 & 6 cm T m 7 3 2 6% 2 3170 0 00 32 m a 4 e a e r 0 S ve 5 m 0 .t 2 2 5 55 m D m a H n .1 0 m a S d u u u u n m u u u u i u m. m m n T m u n u n K O I I 1 C A B CB 0 5 0 1 1 2 1 1 9 I 2 L 4" 6 m m 2 2 I llrlll lllll 33033351 50 9876 826 9 7 7 5 1 96 i2 9982 9874 %Wm%m %m 05055050550 050 505055 0752 .07 e a 5321253-mm2 m 2m 2 6 6 1 1 fl t (I l u u n n I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I n I I I I n n n I I I I n n H B B n u E P P m S u n t m m m n. P A B C A B Table VI shows that in this test compound A has a rapidity of action 9 times greater than that of compound 0 plus PB- .....l

42.4 B and compound C is 4.3 times more active than compound B.

K sm

Percent Dose in dead after DLao, rug/liter 7days p.p.m.

Percent KD TABLE VIIA Dose in p.p.m.

Table VII gives the results of the same test in presence of synergist.

TABLE VII Table VII shows that compound A in the synergistic mixture used in the test is about 22 times more active an compound B in the synergistic mixture.

B. Protection of Stored Grain.--In this test g. of wheat infested with 50 Sitophilus granarius were sprayed with one ml. of the test compound dissolved in a 1:1 mixture of acetone and water with 10 parts by weight of piperonyl butoxide as synergist. After 7 days, the percent mortality was determined. As comparison, S-benzyl- 3-furyl-methyl 3,3-dimethyl-2R-(2' methyl-l-propenyl cyclopropane-IR-carboxylate (compound D) was included in the test. The results are reported in Table VIIA.

Compound D plus PB Doses in m lit r he compounds with and without 10 parts by weight of piperonyl butoxide were directly sprayed in 0.2 ml. solution in a 1:1 aceh chamber. 50 flies were used in each test and the test was repeated -3 times for each dose. The number of dead insects was 10 15 KTsn, min. min. min. min. min. min. mu.

Compound Aplus PBl0 B plus PB10.

d B with a synergist. In a third test with female house flies, t

TABLE V Percent KD afterd the results are reported in Tables V and VI.

Dose in mg./ liter Table IV shows that in this test compounds and B have about the same lethal activity with and without a nergist and that compound C with a synergist 1s more 55 th determined 2, 4, 6, 8, 10 and 15 minutes after the sprayactive than compoun tone-kerosene mixture in the Kearns and Marc ing an Compound A plus PB.

Contr l B plus PB- Table VIII shows that compound A is 1.5 times more active than compound D.

25 Sitophilus granarius for each dose had 0.2 microliters of the test compounds in acetone and 10 parts by weight of piperonyl butoxide applied topically to their ventral thorax and the test was repeated 3 times. The percent dead was determined 1.2 and 6 days after the treatment and the results are reported in Table VIII.

TABLE VIII Percent KD after- Dose in D1150, Compound mg./liter 1 day 2 days 6 days mgJl.

250 100 100 98. 6 plus PB 200 100 109 99.3 54. 3

150 100 98. 7 96. 6 100 99. 3 94. 0 83. 9 250 100 97. 9 98. 6 A plus PB 200 99. 3 89. 3 84. 132. 5

150 85. 5 61. 8 56. 7 100 75. 7 34. 9 26. 7 250 84. 7 75. 3 69. 6 B plus PB 200 69. 0 46. 1 44. 0 210 150 30. 0 15. 3 41. 9 100 10. 8 1. 4 1. 4 Controls 0 O 0 0 Table VIII shows that compound A is 1.58 times more effective than compound B while compound C is 3.85 times more eifective than compound B against Sitophilus granarius.

C. Protection of growing crops-This test was effected by applying 4 microliters of an acetone solution of the test compound on pallets of salad leaves 10 mm. in diameter. 10 Caterpillars were used for each test. The percent mortality was determined 24 and 48 hours after treatment and the results are reported in Table IX.

TABLE IX Percent killed after Compound mg./l. 24 hours 48 hours Controls 0 0 0 wherein X is selected from the group consisting of oxygen and sulfur and R is selected from the group consisting of alkyl of 1 to 6 carbon atoms, a radical of the formula om-iitem-Y.

1 6 I v 1 wherein Y is phenyl, and a radical of the formula om z tacting insects with an insecticidally effective amount of a compound selected from the group consisting of optically active and racemic mixtures of a compound of the formula wherein X is selected from the group consisting of oxygen and sulfur and R is selected from the group consisting of alkyl of 1 to 6 carbon atoms, a radical of the formula wherein Y is phenyl and a radical of the formula wherein Z isselected from the group consisting of alkenyl of 2 to 7 carbon atoms and alkadienyl of 4 to 7 carbon atoms.

5. The method of claim 4 wherein piperonyl butoxide is also present as a synergist in a synergistic amount.

6. The method of claim 4 wherein X is oxygen.

7. The method of claim 4 wherein the compound is the 5-benzyl-3-furyl-methyl ester of trans 3,3-dimethyl-2-(2'- oxo-3'-oxa-cyclopentylidenemethyl) 1 cyclopropanecarboxylic (1R,2R) acid.

8. The method of claim 4 wherein the compound is the 5-benzyl-3-furylnmethyl ester of cis 3,3-dimethyl-2-(2'- oxo- -oxa-cyclopentylidenemethyl) 1 cyclopropanecarboxylic (1R,2S) acid.

9. The method of claim 4 wherein the compound is the di allethrolone ester of trans 3,3 dimethyl 2 (2-oxo- 3' oxa cyclopentylidenemethyl) 1 cyclopropan'e carboxylic (1R,2'R) acid. r

10. The method of claim 4 wherein the compound is di allethrolone ester of cis 3,3 dimethyl 2 (2-oxo- 3 oxa cyclopentylidenemethyl) 1 cyclopropanecarboxylic (1R,2'S) acid.

11. The method of claim 4 wherein the compound is the 5-benzyl-3-furyl-methyl ester of cis 3,3-dimethyl-2-(2'- oxo-3'-thia-cyclopentylidenemethyl) 1 cyclopropanecarb'oxylic (1R,2'S) acid.

12. The method of claim 4 wherein the compound is the S-benzyl-3-furyl-methyl-ester of trans 3,3-dimethyl-2-(2'- oxo 3' thia-cyclopentylidenemethyl) 1 cyclopropanecarboxylic (1R,2R) acid.

17 18 13. A method of combatting household insects which of optically active and racemic mixtures of a compound comprises contacting household insects with an insectiof the formula cidally effective amount of a compound selected from the CH: H group consisting of optically active and racemic mixtures I 1 000R of a compound of the formula 5 cm- (|JH 033 H CH 7 H 0 c 0 CH3 0-H 10 11 H2 g wherein X is selected from the group consisting of oxygen and sulfur and R is selected from the group consisting of f alkyl of 1 to 6 carbon atoms, a radical of the formula mo X 15 C C -cn,-fl itcnryl wherein X is selected from the group consisting of oxygen and sulfur and R is selected from the group consisting of 0 alkyl of 1 to 6 carbon atoms, a radical of the formula h i Y i phenyl d a radical of the f r ul oo Z -cH,-H HCH2Y I 1 wherein Z is selected from the group consisting of alkenyl wherem Y3 ls Phenyl and a radical of the formula of 2 to 7 carbon atoms and alkadienyl of 4 to 7 carbon atoms. CH3 2 References Cited C=C UNITED STATES PATENTS /H( 3\ /(IJ=O 3,714,153 1/1973 Martel et a1 260--240 R g, FOREIGN PATENTS 1,580,475 7/1969 France. 94 309 6/1969 France 260-240 whereln Z is selected from the group consisting of alkenyl of 2 to 7 carbon atoms and alkadienyl of 4 to 7 carbon 1505423 6/1967 France 260 240 amms- VINCENT D. TURNER, Primary Examiner 14. A method of protecting growing crops from insects comprising spraying growing crops with an insecticidal CL amount of a compound selected from the group consisting 424 275 23 2 5 

1. AN INSECTIDAL COMPOSITION COMPRISING AN INSECTICIDALLY EFFECTIVE AMOUNT OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OFF OPTICALLY ACTIVE AND RACEMIC MIXTURES OF A COMPOUND OF THE FORMULA 